Photographic light sensitive material containing copolymer layer

ABSTRACT

A light-sensitive photographic material having at least one layer containing a copolymer represented by the general formula:   WHEREIN R1 and R3 can be H or CH3, R2 can be an alkyl group having one to three carbon atoms, x and y represent positive integers, and Z represents one of:   WHERE N IS 1-3, EXHIBITS REDUCED CURLING UPON EXPOSURE TO MOISTURE.

United States Patent 11 1 Nishio et al.

11] 3,713,829 {451 Jan. 30, 1973 [54] PHOTOGRAPHIC LIGHT SENSITIVE MATERIAL CONTAINING COPOLYMER LAYER [75] Inventors: Fumihiko Nishio; Daijiro Nishio;

S we a aisr ni Qh 9 qk Nakajima, Minami-Ashigara'Machi, Japan [73] Ass ignee: Fuji Photo Film Co., Ltd., Minami- A'shigara-shi, Kanagawa, Japan 22 Filed: Sept. 30, 1971 211 Appl.No.: 188,701

Related.U.S. Application Data [63] Continuation-impart of Ser. No. 554,048, May 31,

I966, abandoned.

[30] Foreign Application Priority Data Primary Examiner-Ronald H. Smith Art0rneySughrue, Rothwell, Mion, Zinn & Macpeak- [57] 1 ABSTRACT general formula:

, i M J; CH2-(5- wherein, R and R can be H or CH R can be an alkyl group having one to three carbon atoms, x and y represent positive integers, and Z represents-one of:

where n is l-3, exhibits reduced curling upon exposure to moisture.

11 Claims, 6 Drawing Figures PATENTED JAN 30 I973 OPTICAL DENSITY EXPOSURE CURL FIGZb 0 CURL VALUE (l0 HGZd ' PIIOTOGRAPIIIC LIGIIT SENSITIVE MATERIAL CONTAINING COPOLYMER LAYER CROSS REFERENCES TO RELATED APPLICATIONS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic silver halide gelatino light-sensitive material containing a copolymer of N-alkoxymethylalkenoylamide, which illustrates improved curling.

2. Description of the Prior Art It is known that in the production of a photographic silver halide light-sensitive emulsion, a naturally occuring or synthetic high molecular compound other than gelatin, such as, poly-N-vinyl lactams, dextrin, laminarine, mannan, hydroxyethylated cellulose, and the like, increases the covering power of the emulsion (the value of the optical density'of the developed emulsion per 1 sq. dm. divided bythe gram number of developed silver per 1 sq. dm.). Accordingly, the contrast, the maximum density, etc can be increased. For example, see US. Pat. Nos. 3,003,878 and 3,058,826; French Patent 1,261,846; and Belgian Patents 611,622 and 6ll,623.

However, as illustrated in FIG. 1 of the accompanying drawing, the sensitivity at the foot portion of the characteristic curve B of the emulsion containing the high molecular weight compound is substantially 'in-. creased as compared with that of the characteristic curve of the emulsion containing no high molecular weight compound.

,Further, it is known that in the production of a photographic silver halide light-sensitive element molecular weight compounds other than gelatin. For

vinyl ether and maleic anhydride or a copolymer of integers;;and Z is one cf the following:

curling is reduced by adding to the silver halide emulsion thereof naturally occurring or synthetic high styrene-and an acrylic ester may be added. Moreover, it I is known that the curling of a photographic light-sensitive element can be reduced by adding a naturally oc- V curring or synthetic high molecular weight compound other than gelatin, such as polyvinyl acetate and av copolymer of butyl acrylate and acrylonitrile, to the undercoating layer. (See French'latent 1,308,399 and GermanPatent 1,081,755).

j The primary object of this invention is to provide a photographic light-sensitive element having low curling characteristics.

A Subsidiary objects of this invention are to provide a 1 photographic light-sensitive silver halide emulsion having'improved sensitivity, maximum density, and contrast.

' :"These and other objects of the invention will become apparent from the following specification and drawing in which:.

,BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph illustrating the improved characteristics obtained with my invention.

FIG. 2 is a schematical representation of various curling values.

SUMMARY OF THE INVENTION trast, and maximum density increased, but also the sensitivity at the footportion in the characteristic curve is increased which indicates the addition of the above compound is a very profitable sensitization.

Furthermore, it has been found thatthe light sensitive e'lernent comprising the emulsion layer containing the above compound has a reduced curling tendency.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The copolymers containing N-alkoxymethylalkenoylamide of the present invention are shown by the following general formula:

r R! R: ca coH.-d .0 ll. 1 5 611120122 wherein R, and R, are H or CH R, is an alkyl group having one to threecarbon atoms; 1: and y are'positive wherein n is 1, 2, or 3, preferably 2.

In a preferred embodiment of the invention 1: is from about 1 to about 50, with y being determined by It is preferred that the proportion of N-alkoxymethyl alkenoylamide be above 30 mol percent.

' In this invention, the copolymers may be used singly or as mixturesthereof. If the polymerization degree of the copolymer is too high, the compatibility thereof with gelatin will bereduced, and hence it isdesirable that the intrinsic viscosity of the copolymer in methanol be less than about 20 at 35C.

Any desired amount of the copolymer may be incorporated in the'emul'sion in this invention, .but the optimum amount thereof forincreasing the sensitivity, gamma value and the maximum density is influenced by the type of photographic silver halide emulsion to be adopted, as well as the use to be made of the product. The proportion of the copolymer containing N-alkoxymethylalkenoylamide may be 340 percent by weight;

preferably, 2 20 percent by weight, based on the.

' ing the curling tendency of a photographic light-sensitive element containing the copolymer is influenced by the kind of support and the thickness of coating, but is generally 3-50 percent by weight. Preferably, l30 percent by weight based on the whole medium of a photographic gelatino silver halide emulsion layer and/or a subsidiary layer (protection' layer, intermediate layer, backlayer, etc.)is used 9 The copolymer may be added in the emulsion at any time, butis most suitably added after the second ripening, and before coating. The copolymer may be added in the emulsion as a powder, but it is convenient to add it as a 10-20 percent aqueous solution thereof.

The present invention is applicable to any kind of silver halide emulsions, such as asilver iodo-bromide emulsion, a silver chloro-bromide emulsion, and the like. The emulsion may be sensitized preliminary with a sulfur and/or a gold compound, and may contain an optical sensitizer, a polyalkyleneoxide type sensitizer, various stabilizers, a hardening agent, a coating aid, a coupler, etc. i

The following are examples of the synthesis of the monomer and the copolymer; however, the invention is not limited to these examples.

SYNTHESIS l A mixture of 303 g. (3 mols.) of N-methylolacrylamide, 1,500 ml. of methanol, and 10 ml. of concentrated hydrochloric acid was heated to 45-50C., and, while stirring, the N methylolacrylamide was dissolved slowly to provide a transparent solution. After continue ing the reaction for 4 hours at the recited temperature, the solution was neutralized with the addition of anhydrous sodium carbonate. After cooling, the salts formed were removed by filtration, and the excess methanol was removed from the filtrate by distillation under reduced'pressure. After the addition of a small amount of hydroquinone as a polymerization inhibitor, the filtrate was subjected to vacuum distillation to provide 290 g. (yield 84 percent) of a colorless liquid having a boiling point of 9395C./lmm.l-lg.

Elementary analysis as C' H,O,N: Calculated N 12.17%;FoundN 11.93%

SYNTHESIS 2 Synthesis of N-Ethoxymethylacrylamide By the same procedure as in Synthesis 1 using a mixture of 303g. (3 mols) of N-methlolacrylamide, 1,500 ml. of ethanol; and ml. of concentrated hydrochloric acid, 330 g. (yield 85- percent) of a colorless liquid having a boiling point"of"l03-l04C./1mm.l-lg was obtained. When the liquid was cooled, a colorlesscrystal (m. p. 2lC.)was form'ecl.

Elementary analysis as C l-[ 0 M Calculated N. 10.85%;Found N 10.55%.

SYNTHESIS 3 Synthesis of N-lsopropoxymethylacrylamide By the same procedure as in Synthesis lusing a mixture of 303 g. (3 mols) of N-methylolacrylamide, 1500 ml. of isopropanol, and 10 ml. of concentrated hydrochloric acid, 351g. (yield 82 percent) of a colorless liquid having a boiling'point of l07-l08C./2mm. Hg was obtained.

Elementary analysis as C H,,,O,N: 9.78%; Found N 10.25%

SYNTHESIS 4 calculated N Synthesis of N-Methoxymethylmethacrylamide By the same procedure as in Synthesis 1 using a mixture of 115 g; (1 mol) of N-methylolmethacrylamide, 500 ml. of methanol and 3.5 ml. of concentrated hydrochloric acid, 103 g. (yield percent) of a colorless liquid having a boiling point of 8385 C/l mm.

Hg was obtained,

Elementary analysis as C H O N: Calculated N 10.85%;FoundN 10.80%.

SYNTHESIS 5 Synthesis'of N-Ethoxymethylmethacrylamide By the same procedure as in Synthesis l using a mixture of g. (1 mol) of N-methylolmethacrylamide, 500 ml. of ethanol and 3.5 ml. of concentrated hydrochloric acid, 11 l g. (yield 78 percent) of a colorlessliquid having a boiling pointof l04.-105C./2 mm. Hg was obtained.

Elementary analysis as C H,,O,N: Calculated N 9.78%; Found N 9.83%

SYNTHESIS6 Synthesis of N-n-Propoxymethylmethacrylamide By the same-procedure as in Synthesis 1, using a mixture of 115g. (1 mol) of N-rnethylolmethacrylicamide, 500 ml. of n-propanol and 3.5 ml. of concentrated hydrochloric acid, I20 g. (yield 72 percent) of a color- I less liquid having a boiling point of l08-l l3C./lmm.

Hg was obtained.

Elementary analysis as C l-l ,O,N: Calculated N 8.38%; Found N 8.71%

SYNTHESIS 7 Other Vinyl Monomers v Copolymerizations of N-ethoxyrnethylacrylarnide with other vinyl monomers in various monomer ratios were carried out under the conditions shown in Table 1 below. When thepolymerization-was carried out in an aqueous phase, polymer separation was conducted by dialyzing the polymer solution with a cellophane diaphragm and subjecting the dialized polymer to freeze drying. When the polymerization was carried out in an organic solvent, the polymer was precipitated by pouring the polymer solution into a large excess of hex-v ane or ether.

TABLE 1 M: (g.) (H) Example M, P lymerizati n p r- (E) (F) (G) per- (I) number (g.) (A) (B) solvent cent) Polymerization initiator 0. min. g. cent [7 1 33.3 N-vinyl 66.7 3/7 Aqueous 35% isopro- 20 2.0 m1. of 30% H O; solution and 40 300 73 73 0, 280

pyrrolldone. panol solution. 0.5 g. of L-ascorbic acid. 2 ..--do-. 46.3 20 -...-do 40 300 s7 37 0.425 3.. 73.0 ..do 27.0 20 .do. 40 300 92 92 0.555 4.-

28.2 Acryloyl 71.8 20 .do 40 240 s3 as 0.455

morpholine. 5 52.2 .do 47.8 20 .d0 4o 2&0 92 92 0.340 6 68.]. do 31.9 20 d0 40 240 90 .90 0.280

Nora: (M N-ethoxymethyl aerylamide, (A) amount of charged monomers, (B) monomer molar ratio, (D) monomer concentration (weight P (E) reaction temperature. (F) Creaction period, (G) amount 0! formed polymer (g.), (H) polymerization conversion (weight percent), (J) intrinsic viscosity [7,] in methanol at 35.0 11

Polymerization conversion shows following formula:

EXAMPLE I A gelatino silver iodo-bromide emulsion for a highsensitive X-ray photographic material containing 480 g. of gelatin and 3.3 mols of silver halide consisting of 1.5 mols of silver iodide and 98.5 mol percent of silver bromide, which had already been ripened to the optimum sensitivity by a sulfur sensitizer and a gold-sensitizer, was divided into 1 l equal parts and each part of the thus divided emulsion was mixed with 60 ml. of a percent aqueous solution of each of a. inactive gelatin,

b. the polymer obtained in Synthesis 7, Experiment No. l,

c. the polymer obtained in Synthesis 7, Experiment No. 2,

d. the polymer obtained in Synthesis 7, Experiment No. 3,

EXAMPLE 2 A silver iodo-bromide emulsion which was the same as in Example 1 was mixed with a copolymer ([1 intrinsic viscosity in methanol*at' 5 was repeated using the thus prepared emulsions. The

e. the polymer obtainedin Synthesis 7, Experiment After addingto each of the emulsions 20ml. of a 1 percent aqueous solution of 4-hydroxyl-6-methyl-l, 3, 3a; 7-tetrazindene as astabilizer, 8 ml. of a 2 percent acetone-aqueous alkali solution of 2, 4-dichloro-6-oxys-triazine as a hardening agent, and 2 ml. of a 4 percent aqueous solution of saponin as a coatingaid, the emulsion was applied on a film based on cellulose triacetate to provide a coating of the same thickness and dried. The photographic light-sensitive film was then exposed for one-twentieth sec. in an actnometer having a blue' filter and then developed for 4 min. at 20C. in a developing solution having the following composition:

N-Methyl-p-aminophenol sulfate 4 Sodium su fite (anhydrous) 66g. Sodium carbonate (mono-hydrate) 53g. Potassium bromide 3 Hydroquinone 13g. Water to make 1 liter.

The photographic densities of the thus develope photographic films are shown in Table II.

increases in sensitivity are shown in Table III. In these cases, an inactive gelatin was added such that the ratio of the silver'halide to the medium was constant.

into 100 g. of a gelatino silver chloride emulsion (the weight ratio of gelatin/silver chloride was 4.5/1) for printing papers was added ml. of a 5 percent aqueous solution of the copolymer of this invention and after the addition of a stabilizer, a coating aid, and a hardening agent, the mixturewas applied to a photo- TABLE II Relative sensitivity Relative sensitivity Gamma Fog giving density giving density of L0. 0.1 on fog on Fog a 100 100 2.23 0.05 b 105 115 2.55 0.05 c 107 1 l5 2.5l 0.04 d 102 l 10 2.47 0 05 e 105 l 15 2.74

graphic paper of g. and dried to provide the dried coating of same thickness in each case.

For comparison, an emulsion containing no polymer of this invention was prepared and applied to a photographic paper by the same conditions to provide a control photographic printing paper.

Theselight-sensitive elements were allowed to stand for minutes at a temperature of 30C. and at a humidity of 30%,RH and then curling was measured, the results of whichare shown in Table [I].

Copolymer of N-ethoxymethylacrylamide (70 mol%) and N-morpholinomethylamide (30 mol%) 4 4 EXAMPLE 4 The purpose of this example was to establish the superiority of the copolymers of the present invention over somewhat similar compounds which are per se known to the prior art, as shown in US. Pat. Nos. 3,360,373 Schaller, 3,341,332 vNakajima and 3,408,199 Saleck.

Preparation of the Samples A 5 percent aqueous solution of each of the following compounds (I-VII) was prepared. To 100 g of a silver chloride emulsion (weight ratio of AgCl to gelatin of 0.84:4; of Ag to gelatin 0.64:4) was added 25 cc of the above-mentioned solution.

The resulting emulsion/solution was coated onto a paper base (document paper used for quick copying; weight 85glm to an Ag amount of 27 glcm (i.e. the coating thickness) and the base was dried. The same base was used with each copolymer. This base was cut into a disc having a cm diameter, and the curling value was measured.

The method of determination of the curling value was as follows:

Cut a disc off from the specimen. The diameter of the disc is 10.0 cm. Punch out a hole in the center of the disc. Fix the center hole of the disc on the top of a bar, which, in turn, is fixed to support. Leave the bar with the specimen disc on its tip in a low humidity atmosphere.

After several hours, the disc curls. The curling value is defined as the minimum distance between peripheries on the opposite sides of the curled disc.

When the disc does not curl, the distance between peripheries on the opposite sides is the disc. The curling value is thus 10.0 (FIG. 2a).

As the disc begins to curl, one pair of peripheries on the opposite sides gets nearer and nearer. The curling value thus becomes smaller; (FIGS. 2b and If the disc continues to curl, a pair of peripheries on the opposite sides contact each other, whereby the curling value is 0.0. (FIG. 2d)

If the disc goes on to curl still more, a-pair of peripheries on the opposite side of the curled disc overlap each other. The curling value becomes negativein value. (FIG. 2e)

For the curling determinations, curling was measured after the discs were cut from the specimens (dried at 50C for 72 hours) and exposed to percent relative humidity at 20C for 24 hours.

Compound I: ScnalIer Pat. (U.S.P.

Compound IIIi'Ihis invention l... lHIO 02115 10 Compound IV: This invention i J, o 00 111K 1 1K zo z s 1) methaerylamide-N-methylol methylether Compound VII: Saleck Pat. polymethacrylamide-N-methylol ethylether \CHrjn Compound No. polymerization ratio curling value I II n l 7.5

III x:y= lzl 9.0

VI n= 1 3.5

Vll n l 3.0 gelatin 6.0

From the data above, where all conditions were equal but the copolymer used, it can be seen that all copolymers in accordance with the present invention provide superior curling (higher positive values), with the order of descending preference being: Compound III; V; IV. It can also be seen that Compounds VI and VII are inferior to the use of gelatin above.

The following claims are to describe the spirit and scope of the present invention, and are not to be taken as limited to the specific examples heretofore set forth.

What is claimed is:

l. A light-sensitive photographic material illustrating a reduced curling tendency comprising a support, at least one photographic silver halide emulsion layer and at least one subsidiary layer, at least one of said emulsion layer and subsidiary layer containing one member Compound VI: Saleck Pat. (U.S.P. 3,408,199) poly- (U.S.P. 3,408,199)

selected from the group consisting of the copolymer represented by the general formula,

wherein R and R each represents a member selected from the group consisting of H and CH R, represents an alkyl group having one to three carbon atoms, 1: and y represent positive integers, and Z represents a member selected from the group consisting of wherein n is l to 3.

2. The photographic light-sensitive material according to claim 1, wherein said support comprises a film.

3. The photographic light-sensitive material according to claim 1, wherein said support comprises a paper.

4. The photographic light-sensitive material according to claim 1, wherein the intrinsic viscosity of said copolymer in methanol at 35C. is less than 2.0.

5. The photographic light-sensitive material according to claim 1 wherein the layer containing said the proportion of the copolymer is 3-50 percent by weight, based on the whole medium in said silver halide emulsion layer.

I copolymer is a silver halide emulsion layer and wherein Cfiz \CO Hr-- H2 10. The p hotographic 1agmseaadvanatemaezra ing to claim 1 wherein Z is 1 1. The photographic light-sensitive material ing to claim 1 wherein Z is a 

1. A light-sensitive photographic material illustrating a reduced curling tendency comprising a support, at least one photographic silver halide emulsion layer and at least one subsidiary layer, at least one of said emulsion layer and subsidiary layer containing one member selected from the group consisting of the copolymer represented by the general formula,
 2. The photographic light-sensitive material according to claim 1, wherein said support comprises a film.
 3. The photographic light-sensitive material according to claim 1, wherein said support comprises a paper.
 4. The photographic light-sensitive material according to claim 1, wherein the intrinsic viscosity of said copolymer in methanol at 35*C. is less than 2.0.
 5. The photographic light-sensitive material according to claim 1 wherein the layer containing said copolymer is a silver halide emulsion layer and wherein the proportion of the copolymer is 3-50 percent by weight, based on the whole medium in said silver halide emulsion layer.
 6. The photographic element of claim 5 where the proportion is 10- 30 percent.
 7. The photographic light-sensitive material according to claim 1 wherein the layer containing said copolymer is a subsidiary layer and the proportion of the copolymer is 3- 50 percent by weight based on the whole medium of the subsidiary layer.
 8. The photographic element of claim 7 where the proportion is 10- 30 percent.
 9. The photographic light-sensitive material according to claim 1 wherein Z is
 10. The photographic light-sensitive material according to claim 1 wherein Z is 